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By integration of benzene-constructed porous organic polymer (KBF) and multiwalled carbon nanotube (MWCNT), a MWCNT-KBF hybrid material was constructed through in situ knitting benzene with formaldehyde dimethyl acetal in the presence of MWCNTs to form a network. MWCNT-KBF was then adopted as a novel solid-phase microextraction (SPME) fiber coating. Coupled to gas chromatography-flame ionization detection, the MWCNT-KBF-assisted SPME method showed large enhancement factors (483-2066), low limits of detection (0.04-0.12 μg L-1), good lin